WO2009148334A1 - Procédé de séparation de gaz - Google Patents

Procédé de séparation de gaz Download PDF

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Publication number
WO2009148334A1
WO2009148334A1 PCT/NZ2009/000097 NZ2009000097W WO2009148334A1 WO 2009148334 A1 WO2009148334 A1 WO 2009148334A1 NZ 2009000097 W NZ2009000097 W NZ 2009000097W WO 2009148334 A1 WO2009148334 A1 WO 2009148334A1
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WO
WIPO (PCT)
Prior art keywords
gas stream
metal oxide
cao
mixture
regenerated
Prior art date
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PCT/NZ2009/000097
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English (en)
Inventor
Stuart Smedley
Vlatko Materic
Carolyn Mary Henderson
Original Assignee
Industrial Research Limited
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Publication date
Application filed by Industrial Research Limited filed Critical Industrial Research Limited
Priority to EP09758581A priority Critical patent/EP2296786A4/fr
Priority to US12/996,501 priority patent/US8383072B2/en
Publication of WO2009148334A1 publication Critical patent/WO2009148334A1/fr
Priority to US13/755,976 priority patent/US9433886B2/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1475—Removing carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/602—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention relates to the separation of CO 2 from gas mixtures. More particularly, the invention relates to a CO 2 separation process in which a sorbent, which is used for absorbing the CO 2 , is recycled.
  • CO 2 Capture and Sequestration is one of the most important of the mitigation options.
  • CCS involves the separation CO 2 from industrial and energy-related sources, transport to a storage location and long-term isolation from the atmosphere. Technologies exist or are under development to capture CO 2 but their cost provides a significant barrier to widespread adoption.
  • CO 2 capture from process streams include the purification of natural gas and production of hydrogen-containing synthesis gas for the manufacture of ammonia, alcohols and synthetic liquid fuels.
  • a disadvantage of all of these processes is that the capacity of natural sorbents (limestones and dolomites) to capture CO 2 typically diminishes rapidly, and a large make-up flow of sorbent (of the order of the mass flow of fuel entering the plant) is required to maintain the CO 2 capture activity in a capture-regeneration loop (J.C. Abanades, E.S. Rubin and EJ. Anthony Ind. Eng. Chem. Res. 43 (2004) 3462-3466). Although the deactivated sorbent may find application in the cement industry and the sorbent cost is low, a range of methods to enhance the activity of calcium-based CO 2 sorbents have been pursued.
  • WO 2005/046863 describes a process for reactivating lime-based sorbents for multiple CO 2 capture cycles during the fluidized bed oxidation of combustion fuels by hydrating the lime after each calcination or by shocking the lime with pure CO 2 .
  • the durability of the sorbents in repetitive CO 2 sorption was recovered by hydration treatment both at ambient temperature and pressure, and at elevated pressure at 200 0 C. However, at elevated pressure, the sorbents melted in repetitive calcination-hydration-carbonation reactions at 923 K and 973 K, most likely because of eutectics in the CaO-Ca(OH) 2 -CaCO 3 ternary system.
  • the present invention provides a process for separating CO 2 from a first gas stream comprising CO 2 , the process comprising the steps of:
  • step (b) contacting the metal oxide with the first gas stream to carbonate the metal oxide and regenerate the metal carbonate; (c) calcining the metal carbonate regenerated in step (b) to regenerate the metal oxide and produce a second product gas stream comprising CO 2 ;
  • step (d) optionally repeating steps (b) and (c) using the metal oxide regenerated in step (c);
  • step (e) contacting the metal oxide regenerated in step (c) with water to form a metal hydroxide
  • step (h) optionally repeating steps (e) to (g) using the metal oxide regenerated in step (g);
  • step (i) contacting the metal oxide regenerated in step (g) with a third gas stream comprising CO 2 to carbonate the metal oxide and regenerate the metal carbonate; Q) optionally repeating steps (c) to (i) using the metal carbonate regenerated in step (i); and (k) repeating steps (a) to (j) using the metal carbonate regenerated in step (i).
  • the present invention provides a process for separating CO 2 from a first gas stream comprising CO 2 , the process comprising the steps of:
  • step (c) calcining the metal carbonate regenerated in step (b) to regenerate the metal oxide and produce a second product gas stream comprising CO 2 ; (d) optionally repeating steps (b) and (c) using the metal oxide regenerated in step (c);
  • step (e) contacting the metal oxide regenerated in step (c) with water to form a metal hydroxide; (f) heating the metal hydroxide in a second gas stream comprising CO 2 to a temperature that is higher than the normal decomposition temperature for the metal hydroxide, and to a temperature and for a time and at a concentration of CO 2 effective to suppress the dehydration of the metal hydroxide and reduce the attrition and fragmentation rates, compared to those that would otherwise occur, of the metal oxide formed upon dehydration of the metal hydroxide;
  • step (h) optionally repeating steps (e) to (g) using the metal oxide regenerated in step (g);
  • step (i) contacting the metal oxide regenerated in step (g) with a third gas stream comprising CO 2 to carbonate the metal oxide and regenerate the metal carbonate;
  • step (j) optionally repeating steps (c) to (i) using the metal carbonate regenerated in step (i);
  • step (k) repeating steps (a) to (j) using the metal carbonate regenerated in step (i).
  • the present invention provides a process for separating CO 2 from a first gas stream comprising CO 2 , the process comprising the steps of: (a) contacting a metal oxide with the first gas stream to carbonate the metal oxide and form a metal carbonate;
  • step (c) repeating steps (a) and (b) using the metal oxide regenerated in step (b); (d) contacting the metal oxide regenerated in step (b) with water to form a metal hydroxide;
  • step (g) repeating steps (a) to (f) using the metal oxide regenerated in step (f).
  • the present invention provides a process for separating CO 2 from a first gas stream comprising CO 2 , the process comprising the steps of:
  • step (b) contacting the metal oxide with the first gas stream to carbonate the metal oxide and regenerate the metal carbonate; (c) calcining the metal carbonate regenerated in step (b) to regenerate the metal oxide and produce a second product gas stream comprising CO 2 ;
  • step (d) optionally repeating steps (b) and (c) using the metal oxide regenerated in step (c);
  • step (e) contacting the metal oxide regenerated in step (c) with water to form a metal hydroxide; (f) heating the metal hydroxide in a second gas stream, wherein the second gas stream comprises a gas effective to suppress the dehydration of the metal hydroxide, to a temperature that is higher than the normal decomposition temperature for the metal hydroxide; (g) dehydrating the metal hydroxide to regenerate the metal oxide;
  • step (h) optionally repeating steps (e) to (g) using the metal oxide regenerated in step (g);
  • step (i) contacting the metal oxide regenerated in step (g) with a third gas stream comprising CO 2 to carbonate the metal oxide and regenerate the metal carbonate;
  • step (j) optionally repeating steps (c) to (i) using the metal carbonate regenerated in step (i); and (k) repeating steps (a) to Q) using the metal carbonate regenerated in step (i).
  • the present invention provides a process for separating CO 2 from a first gas stream comprising CO 2 , the process comprising the steps of:
  • step (c) calcining the metal carbonate regenerated in step (b) to regenerate the metal oxide and produce a second product gas stream comprising CO 2 ;
  • step (d) optionally repeating steps (b) and (c) using the metal oxide regenerated in step (c); (e) contacting the metal oxide regenerated in step (c) with water to form a metal hydroxide;
  • the second gas stream comprises a gas effective to suppress the dehydration of the metal hydroxide, to a temperature that is higher than the normal decomposition temperature for the metal hydroxide, and to a temperature and for a time and at a concentration of the gas effective to suppress the dehydration of the metal hydroxide and reduce the attrition and fragmentation rates, compared to those that would otherwise occur, of the metal oxide formed upon dehydration of the metal hydroxide;
  • step (h) optionally repeating steps (e) to (g) using the metal oxide regenerated in step (g); (i) contacting the metal oxide regenerated in step (g) with a third gas stream comprising CO 2 to carbonate the metal oxide and regenerate the metal carbonate;
  • the present invention provides a process for producing a metal oxide by dehydrating a metal hydroxide, the process comprising heating the metal hydroxide in a gas stream, wherein the gas stream comprises a gas effective to suppress the dehydration of the metal hydroxide, to a temperature higher than the normal dehydration temperature for the metal hydroxide, and dehydrating the metal hydroxide to obtain the metal oxide.
  • the present invention provides a process for restoring the ability of a metal oxide to react with CO 2 , wherein the metal oxide is used in a cyclic process, wherein the metal oxide is reacted with CO 2 to form a metal carbonate and the metal carbonate is calcined to regenerate the metal oxide, the process comprising the steps of: (a) contacting the metal oxide with water to form a metal hydroxide;
  • the present invention also provides apparatus adapted to perform a process of the invention.
  • This invention may also be said broadly to consist in the parts, elements and features referred to or indicated in the specification of the application, individually or collectively, and any or all combinations of any two or more said parts, elements or features, and where specific integers are mentioned herein which have known equivalents in the art to which this invention relates, such known equivalents are deemed to be incorporated herein as if individually set forth.
  • gas concentrations in this specification are expressed as mol%.
  • Figure 1 shows a schematic diagram of a fluidized bed reactor useful for a reaction cycling regime using CaO as a CO 2 sorbent
  • Figure 2 shows a calcination-hydration-dehydration-carbonation reaction cycling regime using CaO as a CO 2 sorbent
  • Figure 3 shows the temperature profile as a function of time for a calcination-hydration- dehydration-carbonation reaction cycle using CaO as a CO 2 sorbent
  • Figure 4 shows a calcination-carbonation reaction cycling regime using CaO as a CO 2 sorbent with intermittent hydration
  • Figure 5 shows the temperature profile as a function of time for a calcination-carbonation reaction cycle using CaO as a CO 2 sorbent
  • Figure 6 shows the cumulative fragmentation for CaO as a CO 2 sorbent over several calcination- hydration-dehydration-carbonation reaction cycles and calcination-carbonation reaction cycles with intermittent hydration;
  • Figure 7 shows a calcination-carbonation reaction cycling regime using CaO as a CO 2 sorbent with intermittent hydration and dehydration under CO 2 ;
  • Figure 8 shows the CO 2 capture activity for CaO as a CO 2 sorbent over several calcination- carbonation reaction cycles with intermittent hydration and calcination-carbonation reaction cycles with intermittent hydration and dehydration under CO 2 ;
  • Figure 9 shows the variation of temperature and the water vapor pressure over a bed of Ca(OH) 2 as a function of time during the heating of the bed under N 2 ;
  • Figure 10 shows the variation of temperature and the water vapor pressure over a bed of Ca(OH) 2 as a function of time during the heating of the bed under N 2 and CO 2 (20%);
  • Figure 11 shows the variation of temperature and the water vapor pressure over a bed of Ca(OH) 2 and temperature as a function of time during the heating of the under N 2 and CO 2 (20%) followed by further heating under N 2 ;
  • Figure 12 shows the dependence Of Ca(OH) 2 dehydration temperature on CO 2 concentration.
  • Hydrating lime at least partially restores its capacity to absorb CO 2 which otherwise reduces with repeated carbonation-calcination cycles.
  • hydrating lime induces structural changes in the material. These changes eventually lead to a weakening of the lime, resulting in significantly increased attrition and fragmentation of the lime sorbent in subsequent carbonation-calcination cycling, especially in fluidized bed reactors. This means that conventional hydration is ineffective in reducing the loss of CO 2 absorption activity during carbonation-calcination cycling, because the CO 2 absorption activity is limited by losses to attrition and fragmentation.
  • the present invention relates to a process for regenerating the CO 2 capture capacity of a metal oxide that is used in a cyclic CO 2 capture process.
  • the present invention further relates to a cyclic process that uses a metal oxide to capture and release CO 2 and that intermittently regenerates the CO 2 capture capacity of the metal oxide to maintain a high capture capacity, with reduced rates of attrition and fragmentation, over many cycles.
  • the present invention also relates to a process for producing a metal oxide from a metal hydroxide, wherein the product metal oxide has an enhanced resistance to attrition and fragmentation.
  • the present invention provides a process for separating CO 2 from a first gas stream comprising CO 2 , the process comprising the steps of: (a) calcining a metal carbonate to generate a metal oxide and produce a first product gas stream comprising CO 2 ;
  • step (b) contacting the metal oxide with the first gas stream to carbonate the metal oxide and regenerate the metal carbonate; (c) calcining the metal carbonate regenerated in step (b) to regenerate the metal oxide and produce a second product gas stream comprising CO 2 ;
  • step (d) optionally repeating steps (b) and (c) using the metal oxide regenerated in step (c);
  • step (e) contacting the metal oxide regenerated in step (c) with water to form a metal hydroxide
  • step (h) optionally repeating steps (e) to (g) using the metal oxide regenerated in step (g);
  • step (i) contacting the metal oxide regenerated in step (g) with a third gas stream comprising CO 2 to carbonate the metal oxide and regenerate the metal carbonate; (j) optionally repeating steps (c) to (i) using the metal carbonate regenerated in step (i); and (k) repeating steps (a) to (j) using the metal carbonate regenerated in step (i).
  • the present invention provides a process for separating CO 2 from a first gas stream comprising CO 2 , the process comprising the steps of:
  • step (c) calcining the metal carbonate regenerated in step (b) to regenerate the metal oxide and produce a second product gas stream comprising CO 2 ; (d) optionally repeating steps (b) and (c) using the metal oxide regenerated in step (c);
  • step (e) contacting the metal oxide regenerated in step (c) with water to form a metal hydroxide
  • step (g) dehydrating the metal hydroxide to regenerate the metal oxide; (h) optionally repeating steps (e) to (g) using the metal oxide regenerated in step (g); (i) contacting the metal oxide regenerated in step (g) with a third gas stream comprising CO 2 to carbonate the metal oxide and regenerate the metal carbonate;
  • step (j) optionally repeating steps (c) to (i) using the metal carbonate regenerated in step (i); and (k) repeating steps (a) to (j) using the metal carbonate regenerated in step (i).
  • the present invention provides a process for separating CO 2 from a first gas stream comprising CO 2 , the process comprising the steps of:
  • step (c) repeating steps (a) and (b) using the metal oxide regenerated in step (b);
  • step (d) contacting the metal oxide regenerated in step (b) with water to form a metal hydroxide
  • step (e) heating the metal hydroxide in a second gas stream comprising CO 2 ;
  • step (f) dehydrating the metal hydroxide in a third gas stream to regenerate the metal oxide; and (g) repeating steps (a) to (f) using the metal oxide regenerated in step (f).
  • a number of metal oxides can be carbonated to form the corresponding metal carbonate that, in turn, can be calcinated to regenerate the metal oxide. Any of these oxides may be used as the CO 2 sorbent in a process of the invention.
  • the metal oxide is selected from the group consisting of: alkali metal oxides; alkaline earth metal oxides; first row transition metal oxides; aluminum oxide; lead oxide; and mixtures of any two or more thereof.
  • the metal oxide is selected from the group consisting of: alkaline earth metal oxides; zinc oxide; manganese oxide; nickel oxide; copper oxide; lead oxide; and mixtures of any two or more thereof.
  • the metal oxide is an alkaline earth metal oxide.
  • the metal oxide is selected from: CaO; MgO; and mixtures thereof.
  • a metal oxide within this embodiment may be formed by calcining dolomite (calcium magnesium carbonate, CaMg(COs) 2 ).
  • the metal oxide is CaO.
  • a metal oxide within this embodiment may be formed by calcining limestone (calcium carbonate, CaCO 3 ).
  • the invention also contemplates embodiments in which the starting material for the third embodiment is a metal carbonate such that the process comprises a preliminary step, before step (a), of calcining the metal carbonate to form the metal oxide.
  • any calcination process may be utilized to calcine the metal carbonate to regenerate the metal oxide and produce a stream of CO 2 .
  • the selection of the temperature at which the metal carbonate is calcined will depend on the pressure, particularly on the partial pressure of CO 2 .
  • the carbonate is calcined by heating to a temperature between about 700°C and about 110O 0 C under a partial pressure of CO 2 that is below the equilibrium pressure. Under these conditions, the carbonate rapidly decomposes to release a stream of CO 2 .
  • the various product gas streams comprising CO 2 gas obtained upon calcination of the metal carbonate may be suitable for direct utilization or, if necessary, may be further purified, for example by scrubbing to remove particulate matter.
  • the product gas streams comprise substantially pure CO 2 .
  • Gas streams comprising CO 2 are well-known in the art and include, but are not limited to: flue gas from combustion processes; syngas of different compositions produced by gasif ⁇ ers; gas outputs from cement kilns and steel production; gas outputs from ammonia synthesis; gas outputs from various biological reactors, including fermenters and digesters; some natural gas; and air.
  • the gas stream comprising CO 2 is a post-combustion gas stream and in other embodiments, the gas stream is a pre-combustion gas stream.
  • the first gas stream comprises CO 2 in a concentration from about 5% to about 100%.
  • the invention is not limited thereto and the first gas stream may comprise CO 2 in a concentration that is outside this range.
  • the first gas stream may comprise ambient air, in which the CO 2 concentration is about 380 ppm.
  • the selection of the temperature at which the metal oxide is contacted with a gas stream comprising CO 2 to carbonate the metal oxide and form the metal carbonate will depend on the pressure, particularly on the partial pressure of CO 2 .
  • the metal oxide is contacted with the gas stream comprising CO 2 at a temperature between about 30O 0 C and about 950 0 C.
  • temperatures outside this range may be used in some embodiments. In particular, higher temperatures may be used where the partial pressure of CO 2 is sufficiently high.
  • the metal oxide is carbonated at a temperature from 600°C to 800°C.
  • the length of time that the metal oxide is contacted with the gas stream comprising CO 2 will also depend on the pressure and temperature of the gas stream. In one embodiment, the metal oxide is contacted with the gas stream comprising CO 2 for 5 minutes to 60 minutes. Time outside this range may be used in other embodiments.
  • the temperature is typically between about 450°C and about 800 0 C.
  • the temperature is typically between about 550 0 C and about 950 0 C.
  • the metal oxide may be contacted with the first gas stream at ambient temperature, or the first gas stream may be compressed and/or heated prior to contacting the metal oxide.
  • Suitable apparatus for performing the process of the invention are well-known.
  • the various process steps may be performed at ambient pressure or, in some embodiments, one or more steps may be performed at elevated or reduced pressure.
  • the metal oxide may be contacted with a gas stream comprising CO 2 or with water using a suitable gas-solid contact reactor.
  • the gas-solid contact reactor comprises a mobile solid phase.
  • the gas-solid contact reactor comprises a fluidized or moving bed.
  • a fluidized or moving bed system may be preferred to: improve the gas-solid contact; facilitate mass transfer in and out of the solid; improve the heat transfer properties of the solid; and facilitate the transfer of the solid from one reaction (reactor) to another.
  • at least one step of a process of the invention is performed in one or more fluidized or moving bed. In another preferred embodiment, all of the steps are performed in one or more fluidized or moving bed.
  • Calcium oxide can be chemically activated for use as a CO 2 sorbent by hydration with water between calcination and carbonation in a cyclic process.
  • hydration of calcium oxide is disadvantageous for its physical properties. Repeated cycling in this manner (carbonation- calcination-hydration-dehydration) causes the material to vesiculate, expand and become very brittle. Hydration alone is, therefore, insufficient to maintain calcium oxide as a viable CO 2 sorbent over many tens of cycles in a fluidized bed reactor.
  • the present invention provides a sequence of steps involving hydration for sorbent activation and thermal treatment of the resulting hydroxide to enhance particle resistance to attrition and fragmentation in the harsh conditions of a fluidized bed.
  • each of the steps in the process of the present invention may be performed in the same fluidized bed, thereby avoiding the inefficiencies associated with moving the sorbent material between a number of different reactors.
  • the invention is not limited thereto and embodiments in which the sorbent material is moved between two or more reactors either between or during the various steps of the process are also contemplated.
  • the invention also includes embodiments in which the sorbent material is held in several reactors and the mass flows into and out of the reactors are controlled to achieve continuous processing of the first gas stream comprising CO 2 .
  • the steps used in the present invention reduce the need to add additional CO 2 sorbent. However, if necessary, fresh sorbent can be added to replace the amount lost from the system as fines or otherwise lost through side reactions such as reaction with other components in the gas stream.
  • the number of times steps (b) and (c) are repeated in step (d) is from 1 to 20. In another embodiment, the number of times steps (b) and (c) are repeated in step (d) is from 2 to 4. In one embodiment of the first and second aspects, the number of times steps (e) to (g) are repeated in step (h) is from 1 to 20. In another embodiment, the number of times steps (e) to (g) are repeated in step (h) is from 1 to 4.
  • step (h) is omitted.
  • the number of times steps (c) to (i) are repeated in step (j) is from 1 to 20. In another embodiment, the number of times steps (c) to (i) are repeated in step (j) is from 1 to 4.
  • step (j) is omitted.
  • the number of times steps (a) and (b) are repeated in step (c) is from 1 to 20. In another embodiment, the number of times steps (a) and (b) are repeated in step (c) is from 2 to 4.
  • the amount of metal oxide retained in the fluidized bed is at least about 85% of the initial amount after 75 calcinations.
  • the amount of metal oxide retained in the fluidized bed is at least about 90% of the initial amount after 75 calcinations.
  • the metal oxide retains an average CO 2 absorption capacity of at least about 40%, measured with respect to the initial capacity, after 75 calcinations.
  • the metal oxide retains an average CO 2 absorption capacity of at least about 55% after 75 calcinations.
  • the metal oxide retains an average CO 2 absorption capacity of at least about 315 g C ⁇ 2 /kg metal oxide after 75 calcinations.
  • the metal oxide retains an average CO 2 absorption capacity of at least about 430 g CO 2 /kg metal oxide after 75 calcinations.
  • the metal oxide may be contacted with water that is either in the liquid phase or is water vapor. In a preferred embodiment, the metal oxide is contacted with water vapor. In some embodiments, the contacting is performed at elevated pressure.
  • the metal oxide is typically contacted with water at a partial pressure above the equilibrium pressure for the formation of the metal hydroxide at the selected hydration temperature.
  • the metal oxide is contacted with water vapor at an absolute humidity from 5% to 100%. In a preferred embodiment, the absolute humidity is from 30% to 43%.
  • the metal oxide is contacted with water vapor at a temperature from 100 0 C to 700°C. In a preferred embodiment, the temperature is from 100 0 C to 450 0 C, more preferably from 100 0 C to 400 0 C, more preferably from 150 0 C to 400 0 C, more preferably from 280 0 C to 380 0 C.
  • the metal oxide is typically contacted with water until the hydration reaction is at least substantially complete.
  • the metal hydroxide is maintained in the presence of the water vapor for a time from 5 to 60 minutes. Preferably, the time is from 15 to 25 minutes.
  • CO 2 is added to the water vapor after the metal oxide has partially or fully hydrated.
  • the water vapor further comprises CO 2 in the range from 0% to 75%.
  • the water vapor further comprises CO 2 in the range from 0 % to 20 %.
  • a metal hydroxide may be dehydrated by heating to a temperature between about 400 0 C and about 700 0 C under a water vapor pressure that is below the equilibrium vapor pressure for the hydroxide at the selected pressure.
  • the metal hydroxide may be dehydrated at a lower temperature, for example down to about 100 0 C, by reducing the pressure at which the dehydration takes place.
  • the sequence of process steps disclosed herein includes thermal treatment of the metal hydroxide to enhance the resistance of the sorbent particles- to attrition and fragmentation in the harsh conditions of a fluidized bed.
  • This thermal treatment involves heating the metal hydroxide in a second gas stream comprising CO 2 .
  • this treatment may be performed at elevated pressure.
  • heating the metal hydroxide in the second gas stream comprising CO 2 enables the metal hydroxide to be heated to a higher temperature than that at which dehydration would be expected to occur — the normal decomposition temperature. Heating the metal hydroxide in an atmosphere comprising CO 2 results in a thermodynamically unstable metal hydroxide.
  • step (e) comprises heating the metal hydroxide to a temperature that is higher than the normal decomposition temperature for the metal hydroxide.
  • normal decomposition temperature means the temperature at which dehydration of the metal hydroxide is observed to occur under an inert atmosphere (such as a N 2 atmosphere) in equivalent apparatus and under equivalent process conditions.
  • process conditions may include the water vapor pressure, total gas flow, reactor size and type (for example, fluidized or static bed), sorbent amount, sorbent particle size, sorbent history, heat flow etc.
  • dehydration will be observed when the metal hydroxide loses water at a rate of about 0.5% w/w per minute.
  • Figure 9 shows that the normal decomposition temperature of Ca(OH) 2 in a stream ofN 2 is about 445 0 C in the apparatus and under the conditions described in the Examples.
  • that decomposition temperature in the same apparatus and under equivalent process conditions increases to: 529°C for a 12.5% CO 2 /N 2 mixture; 543°C for a 25% CO 2 ZN 2 mixture; 611 0 C for a 37.5% CO 2 /N 2 mixture; 619°C for a 70% CO 2 /N 2 mixture; and 620 0 C for 100% CO 2 gas.
  • thermodynamically unstable metal hydroxide produces a metal oxide that has lower attrition and fragmentation rates during subsequent cycling in a fluidized bed reactor than the metal oxide produced by conventional dehydration.
  • the increased mechanical strength of the metal oxide is thought to arise from maintaining the metal hydroxide in a thermodynamically unstable state, at temperatures higher than normal metal hydroxide decomposition temperature. It is thought that, at these temperatures, a process akin to annealing occurs, where the strains and crystal defects formed during hydration of the metal oxide are healed. The extent of healing may, therefore, be proportional to both the temperature and the time spent by the metal hydroxide in the thermodynamically unstable state.
  • the second gas stream comprising CO2 is the same as the first gas stream.
  • the invention also includes embodiments in which the second gas stream comprises a different concentration of CO 2 -
  • the first gas stream may be enriched or depleted in CO 2 to provide the second stream.
  • the second gas stream may be substantially pure CO 2 .
  • the various product gas streams comprising CO 2 gas obtained upon calcination of the metal carbonate may be recycled to provide the CO 2 used in the second gas stream.
  • the second gas stream comprises CO 2 from the first and/or second product gas streams.
  • the second gas stream comprises 5% to 100% CO 2 . In a preferred embodiment, the second gas stream comprises 20% to 100% CO 2 , more preferably 30% to 100% CO 2 , more preferably 37.5% to 100% CO 2 .
  • the second gas stream comprises a CO 2 concentration selected from: 12.5%; 25%; 37.5%; 70% and 100%.
  • the second gas stream comprising CO 2 further comprises water vapor.
  • the metal hydroxide is heated to a temperature that is at least about 10 0 C higher than the normal decomposition temperature for the metal hydroxide.
  • the temperature is at least about 20°C higher than the normal decomposition temperature for the metal hydroxide; at least about 3O 0 C higher; at least about 40 0 C higher; at least about 5O 0 C higher; at least about 60 0 C higher; at least about 7O 0 C higher; at least about 80 0 C higher; at least about 90 0 C higher; at least about 100 0 C higher; at least about 110 0 C higher; at least about 12O 0 C higher; at least about 130 0 C higher; at least about 140 0 C higher; at least about 150 0 C higher; at least about 160 0 C higher; or at least about 170 0 C higher.
  • the metal hydroxide is heated to a temperature that is at least about 5O 0 C higher than the normal decomposition temperature for the metal hydroxide.
  • the temperature difference between the normal decomposition temperature of the metal hydroxide and the temperature to which the metal hydroxide is heated is selected from: 1O 0 C; 15°C; 20 0 C; 25°C; 30 0 C; 35°C; 4O 0 C; 45 0 C; 50°C; 55°C; 60 0 C; 65°C; 70 0 C; 75°C; 80°C; 85 0 C; 90°C; 95°C; 100°C; 105 0 C; 110 0 C; 115°C; 12O 0 C; 125°C; 130 0 C; 135°C; 140 0 C; 145°C; 150 0 C; 155°C; 160 0 C; 165°C; 170 0 C; 175°C; and any subgroup thereof.
  • the upper limit of the temperature to which the metal hydroxide is heated is that temperature at which the metal hydroxide inevitably loses water to form the metal oxide.
  • the time the metal hydroxide spends in the thermodynamically unstable state is determined by the heating rate during any temperature increase and the length of any time at which the temperature is held constant.
  • the metal hydroxide is heated at a rate of temperature increase from 1 °C/min to 50°C/min. In a preferred embodiment, the rate of temperature increase is from 3°C/min to 18°C/min. In another preferred embodiment, the rate of temperature increase is 13°C/min.
  • the metal hydroxide is heated to a temperature from 500 0 C to 620 0 C. In another preferred embodiment, the temperature is from 500 0 C to 600 0 C
  • the metal hydroxide is held at a constant temperature above the normal decomposition temperature for a period of time.
  • the temperature is from 500 0 C to 620 0 C.
  • the temperature is from 500 0 C to 600 0 C.
  • the temperature is 520 0 C.
  • the time is from 5 minutes to 300 minutes.
  • the time is from 5 minutes to 60 minutes.
  • the time is from 10 minutes to 50 minutes.
  • the time is from 20 minutes to 40 minutes.
  • the time is 23 minutes.
  • the total time spent by the metal hydroxide at a temperature that is higher than the normal decomposition temperature for the metal hydroxide is at least about 10 minutes.
  • the metal hydroxide is dehydrated to regenerate the metal oxide.
  • the metal hydroxide is heated to a temperature from 500 0 C to 800 0 C to dehydrate the metal hydroxide and regenerate the metal oxide.
  • the temperature is from 600 0 C to 700 0 C.
  • the metal hydroxide may be dehydrated to regenerate the metal oxide by substituting the second gas stream comprising CO 2 with a fourth gas stream in the first and second aspects.
  • the metal hydroxide is dehydrated to regenerate the metal oxide by substituting the second gas stream comprising CO 2 with a third gas stream.
  • the fourth gas stream of the first and second aspects, and the third gas stream of the third aspect has a concentration of CO 2 such that the metal hydroxide dehydrates at the temperature at which that gas stream substitutes for the second gas stream.
  • the fourth gas stream of the first and second aspects, and the third gas stream of the third aspect does not include CO 2 or comprises a low concentration Of CO 2 , for example ambient air.
  • the fourth gas stream of the first and second aspects, and the third gas stream of the third aspect comprises less than about 15% CO 2 .
  • the gas stream comprises less than about 10% CO 2 , less than about 5% CO 2 , or less than about 2% CO 2 , or less than about 1 % CO 2 .
  • the invention also contemplates embodiments in which the process ends at this stage, to provide a metal oxide product having an enhanced resistance to attrition and fragmentation.
  • the metal oxide product may also comprise some metal carbonate.
  • the fourth gas stream is the same as the third gas stream in which the resulting metal oxide is then carbonated, as described below.
  • the metal hydroxide may be further heated in the second gas stream comprising CO 2 until the dehydration temperature, which is a function of the water vapor pressure and CO 2 concentration, is reached.
  • the resulting metal oxide is then carbonated in a third gas stream comprising CO 2 to regenerate the metal carbonate.
  • This carbonation reaction may be performed as described above.
  • the third gas stream of the first and second aspects may be a separate gas stream that comprises CO 2 .
  • the third gas stream is the same as the first gas stream.
  • the metal oxide captures further CO 2 from the first gas stream, which is then released as part of the first product gas stream when the cyclical process is repeated.
  • the third gas stream of the first and second aspects is the same as the second gas stream.
  • the metal hydroxide may be further heated in the second gas stream until it dehydrates. The temperature is then maintained or increased to carbonate the metal oxide.
  • the metal oxide captures at least part of this added CO 2 , which is then released as part of the first product gas stream when the cyclical process is repeated.
  • a preferred embodiment of the invention comprises a process for separating CO 2 from a first gas stream comprising CO 2 , the process comprising the steps of:
  • step (c) calcining the metal carbonate regenerated in step (b) to regenerate the metal oxide and produce a second product gas stream comprising CO 2 ;
  • step (d) optionally repeating steps (b) and (c) using the metal oxide regenerated in step (c);
  • step (e) contacting the metal oxide regenerated in step (c) with water to form a metal hydroxide; (f) heating the metal hydroxide in a second gas stream comprising CO 2 to a temperature that is higher than the normal decomposition temperature for the metal hydroxide; (g) dehydrating the metal hydroxide to regenerate the metal oxide; (h) contacting the metal oxide regenerated in step (g) with a third gas stream comprising CO 2 to carbonate the metal oxide and regenerate the metal carbonate; and (i) repeating steps (a) to (h) using the metal carbonate regenerated in step (h).
  • a further preferred embodiment of the invention comprises a process for separating CO 2 from a first gas stream comprising CO 2 , the process comprising the steps of:
  • step (c) calcining the metal carbonate regenerated in step (b) to regenerate the metal. oxide and produce a second product gas stream comprising CO 2 ;
  • step (d) optionally repeating steps (b) and (c) using the metal oxide regenerated in step (c); (e) contacting the metal oxide regenerated in step (c) with water to form a metal hydroxide;
  • step (g) dehydrating the metal hydroxide to regenerate the metal oxide; (h) contacting the metal oxide regenerated in step (g) with a third gas stream comprising CO 2 to carbonate the metal oxide and regenerate the metal carbonate; and (i) repeating steps (a) to (h) using the metal carbonate regenerated in step (h).
  • Another preferred embodiment of the invention comprises a process for separating CO 2 from a first gas stream comprising CO 2 , the process comprising the steps of: (a) calcining CaC ⁇ 3 to generate CaO and produce a first product gas stream comprising CO 2 ;
  • step (c) calcining the CaCO 3 regenerated in step (b) to regenerate the CaO and produce a second product gas stream comprising CO 2 ;
  • step (d) optionally repeating steps (b) and (c) using the CaO regenerated in step (c);
  • step (e) contacting the CaO regenerated in step (c) with water to form Ca(OH) 2 ;
  • step (h) optionally repeating steps (e) to (g) using the CaO regenerated in step (g);
  • step (i) contacting the CaO regenerated in step (g) with a third gas stream comprising CO 2 to carbonate the CaO and regenerate the CaCO 3 ;
  • step (j) optionally repeating steps (c) to (i) using the CaCO 3 regenerated in step (i); and (k) repeating steps (a) to (j) using the CaCO 3 regenerated in step (i).
  • Another preferred embodiment of the invention comprises a process for separating CO 2 from a first gas stream comprising CO 2 , the process comprising the steps of:
  • step (c) calcining the CaCO 3 regenerated in step (b) to regenerate the CaO and produce a second product gas stream comprising CO 2 ; (d) optionally repeating steps (b) and (c) using the CaO regenerated in step (c);
  • step (e) contacting the CaO regenerated in step (c) with water to form Ca(OH) 2 ;
  • step (h) optionally repeating steps (e) to (g) using the CaO regenerated in step (g); (i) contacting the CaO regenerated in step (g) with a third gas stream comprising CO 2 to carbonate the CaO and regenerate the CaCO 3 ;
  • step Q) optionally repeating steps (c) to (i) using the CaCO 3 regenerated in step (i); and (k) repeating steps (a) to Q) using the CaCO 3 regenerated in step (i).
  • Another preferred embodiment of the invention comprises a process for separating CO 2 from a first gas stream comprising CO 2 , the process comprising the steps of:
  • step (b) contacting the mixture of CaO and MgO with the first gas stream to carbonate the mixture of CaO and MgO and regenerate the mixture Of CaCO 3 and MgCO 3 ; (c) calcining the mixture of CaCO 3 and MgCO 3 regenerated in step (b) to regenerate the mixture of CaO and MgO and produce a second product gas stream comprising CO 2 ;
  • step (d) optionally repeating steps (b) and (c) using the mixture of CaO and MgO regenerated in step (c);
  • step (e) contacting the mixture of CaO and MgO regenerated in step (c) with water to form a mixture of Ca(OH) 2 and Mg(OH) 2 ;
  • step (h) optionally repeating steps (e) to (g) using the mixture of CaO and MgO regenerated in step (g); (i) contacting the mixture of CaO and MgO regenerated in step (g) with a third gas stream comprising CO 2 to carbonate the mixture of CaO and MgO and regenerate the mixture of CaCO 3 and MgCO 3 ;
  • step (j) optionally repeating steps (c) to (i) using the mixture of CaCO 3 and MgCO 3 regenerated in step (i);
  • step (k) repeating steps (a) to Q) using the mixture of CaCO 3 and MgCO 3 regenerated in step (i).
  • Another preferred embodiment of the invention comprises a process for separating CO 2 from a first gas stream comprising CO 2 , the process comprising the steps of:
  • step (c) calcining the mixture of CaCO 3 and MgCO 3 regenerated in step (b) to regenerate the mixture of CaO and MgO and produce a second product gas stream comprising CO 2 ; (d) optionally repeating steps (b) and (c) using the mixture of CaO and MgO regenerated in step (c);
  • step (e) contacting the mixture of CaO and MgO regenerated in step (c) with water to form a mixture Of Ca(OH) 2 and Mg(OH) 2 ;
  • step (h) optionally repeating steps (e) to (g) using the mixture of CaO and MgO regenerated in step (g); (i) contacting the mixture of CaO and MgO regenerated in step (g) with a third gas stream comprising CO 2 to carbonate the mixture of CaO and MgO and regenerate the mixture of CaCO 3 and MgCO 3 ; (j) optionally repeating steps (c) to (i) using the mixture of CaCO 3 and MgCO 3 regenerated in step (i); and (k) repeating steps (a) to (j) using the mixture of CaCO 3 and MgCO 3 regenerated in step (i).
  • Another preferred embodiment of the invention comprises a process for separating CO 2 from a first gas stream comprising CO 2 , the process comprising the steps of:
  • step (b) contacting the CaO with the first gas stream to carbonate the CaO and regenerate the CaCO 3 ; (c) calcining the CaCO 3 regenerated in step (b) to regenerate the CaO and produce a second product gas stream comprising CO 2 ;
  • step (d) optionally repeating steps (b) and (c) using the CaO regenerated in step (c);
  • step (e) contacting the CaO regenerated in step (c) with water to form Ca(OH) 2 ;
  • step (h) contacting the CaO regenerated in step (g) with a third gas stream comprising CO 2 to carbonate the CaO and regenerate the CaCO 3 ; (i) repeating steps (a) to (h) using the CaCO 3 regenerated in step (h).
  • Another preferred embodiment of the invention comprises a process for separating CO 2 from a first gas stream comprising CO 2 , the process comprising the steps of:
  • step (c) calcining the CaCO 3 regenerated in step (b) to regenerate the CaO and produce a second product gas stream comprising CO 2 ;
  • step (d) optionally repeating steps (b) and (c) using the CaO regenerated in step (c);
  • step (e) contacting the CaO regenerated in step (c) with water to form Ca(OH) 2 ;
  • step (h) contacting the CaO regenerated in step (g) with a third gas stream comprising CO 2 to carbonate the CaO and regenerate the CaCO 3 ;
  • step (i) repeating steps (a) to (h) using the CaC ⁇ 3 regenerated in step (h).
  • Another preferred embodiment of the invention comprises a process for separating CO 2 from a first gas stream comprising CO 2 , the process comprising the steps of:
  • step (c) calcining the CaCO 3 regenerated in step (b) to regenerate the CaO and produce a second product gas stream comprising CO 2 ; (d) optionally repeating steps (b) and (c) using the CaO regenerated in step (c);
  • step (e) contacting the CaO regenerated in step (c) with water vapor at an absolute humidity from 5% to 100% and at a temperature from 10O 0 C to 700°C to form Ca(OH) 2 ;
  • step (f) heating the Ca(OH) 2 in a second gas stream comprising from 20% to 100% CO 2 to a temperature from 500°C to 620°C;
  • step (g) dehydrating the Ca(OH) 2 to regenerate the CaO by heating the Ca(OH) 2 to a temperature from 600 0 C to 700°C;
  • step (h) contacting the CaO regenerated in step (g) with a third gas stream comprising CO 2 to carbonate the CaO and regenerate the CaCO 3 ;
  • step (i) repeating steps (a) to (h) using the CaCO 3 regenerated in step (h).
  • Another preferred embodiment of the invention comprises a process for separating CO 2 from a first gas stream comprising CO 2 , the process comprising the steps of:
  • step (c) calcining the CaCO 3 regenerated in step (b) to regenerate the CaO and produce a second product gas stream comprising CO 2 ;
  • step (d) optionally repeating steps (b) and (c) using the CaO regenerated in step (c); (e) contacting the CaO regenerated in step (c) with water vapor at an absolute humidity from 5% to 100% and at a temperature from 100°C to 700 0 C to form Ca(OH) 2 ;
  • step (f) heating the Ca(OH) 2 in a second gas stream comprising from 20% to 100% CO 2 to a temperature from 500 0 C to 600 0 C;
  • step (g) dehydrating the Ca(OH) 2 to regenerate the CaO in a gas stream comprising less than about 15% CO 2 ;
  • step (h) contacting the CaO regenerated in step (g) with a third gas stream comprising CO 2 to carbonate the CaO and regenerate the CaCO 3 ;
  • step (i) repeating steps (a) to (h) using the CaCO 3 regenerated in step (h).
  • Another preferred embodiment of the invention comprises a process for separating CO 2 from a first gas stream comprising CO 2 , the process comprising the steps of:
  • step (c) calcining the MgCO 3 regenerated in step (b) to regenerate the MgO and produce a second product gas stream comprising CO 2 ;
  • step (d) optionally repeating steps (b) and (c) using the MgO regenerated in step (c);
  • step (e) contacting the MgO regenerated in step (c) with water to form Mg(OH) 2 ;
  • step (f) heating the Mg(OH) 2 in a second gas stream comprising CO 2 to a temperature that is higher than the normal decomposition temperature for Mg(OH) 2 ;
  • step (h) contacting the MgO regenerated in step (g) with a third gas stream comprising CO 2 to carbonate the MgO and regenerate the MgCO 3 ; (i) repeating steps (a) to (h) using the MgCO 3 regenerated in step (h).
  • Another preferred embodiment of the invention comprises a process for separating CO 2 from a first gas stream comprising CO 2 , the process comprising the steps of:
  • step (a) calcining a mixture of CaCO 3 and MgCO 3 to generate a mixture of CaO and MgO and produce a first product gas stream comprising CO 2 ;
  • step (b) contacting a mixture of CaO and MgO with the first gas stream to carbonate the mixture of CaO and MgO and regenerate the mixture of CaCO 3 and MgCO 3 ;
  • step (c) calcining the mixture of CaCO 3 and MgCO 3 regenerated in step (b) to regenerate the mixture of CaO and MgO and produce a second product gas stream comprising CO 2 ;
  • step (d) optionally repeating steps (b) and (c) using the mixture of CaO and MgO regenerated in step (c);
  • step (e) contacting a mixture of CaO and MgO regenerated in step (c) with water to form a mixture of Ca(OH) 2 and Mg(OH) 2 ;
  • step (f) heating the mixture of Ca(OH) 2 and Mg(OH) 2 in a second gas stream comprising CO 2 to a temperature that is higher than the normal decomposition temperature for the mixture of Ca(OH) 2 and Mg(OH) 2 ;
  • step (h) contacting the mixture of CaO and MgO regenerated in step (g) with a third gas stream comprising CO 2 to carbonate the mixture of CaO and MgO and regenerate the mixture of CaCO 3 and MgCO 3 ; (i) repeating steps (a) to (h) using the mixture Of CaCO 3 and MgCO 3 regenerated in step (h).
  • Another preferred embodiment of the invention comprises a process for separating CO 2 from a first gas stream comprising CO 2 , the process comprising the steps of:
  • step (b) contacting a mixture of CaO and MgO with the first gas stream to carbonate the mixture of CaO and MgO and regenerate the mixture Of CaCO 3 and MgCO 3 ; (c) calcining the mixture of CaCO 3 and MgCO 3 regenerated in step (b) to regenerate the mixture of CaO and MgO and produce a second product gas stream comprising CO 2 ;
  • step (d) optionally repeating steps (b) and (c) using the mixture of CaO and MgO regenerated in step (c);
  • step (e) contacting a mixture of CaO and MgO regenerated in step (c) with water to form a mixture of Ca(OH) 2 and Mg(OH) 2 ;
  • step (h) contacting the mixture of CaO and MgO regenerated in step (g) with a third gas stream comprising CO 2 to carbonate the mixture of CaO and MgO and regenerate the mixture of CaCO 3 and MgCO 3 ;
  • step (i) repeating steps (a) to (h) using the mixture of CaC ⁇ 3 and MgCO 3 regenerated in step (h).
  • Another preferred embodiment of the invention comprises a process for separating CO 2 from a first gas stream comprising CO 2 , the process comprising the steps of:
  • step (c) calcining the mixture of CaCO 3 and MgCO 3 regenerated in step (b) to regenerate the mixture of CaO and MgO and produce a second product gas stream comprising CO 2 ;
  • step (d) optionally repeating steps (b) and (c) using the mixture of CaO and MgO regenerated in step (c);
  • step (e) contacting the mixture of CaO and MgO regenerated in step (c) with water vapor at an absolute humidity from 5% to 100% and at a temperature from 100°C to 700 0 C to form s a mixture of Ca(OH) 2 and Mg(OH) 2 ;
  • step (g) dehydrating the mixture of Ca(OH) 2 and Mg(OH) 2 to regenerate the mixture of CaO and MgO by heating the mixture of Ca(OH) 2 and Mg(OH) 2 to a temperature from 600°C to 700°C; (h) contacting the mixture of CaO and MgO regenerated in step (g) with a third gas stream comprising CO 2 to carbonate the mixture of CaO and MgO and regenerate the mixture of CaCO 3 and MgCO 3 ; (i) repeating steps (a) to (h) using the mixture of CaCO 3 and MgCO 3 regenerated in step (h).
  • Chemisorbed water may be formed in the presence of CO 2 gas during the dehydration of the Ca(OH) 2 , which may result in the significant elevation of the decomposition temperature observed in the Examples.
  • the present applicants have determined that, in the presence of a gas effective to suppress the dehydration of the metal hydroxide, the temperature at which the metal hydroxide dehydrates is elevated with respect to the dehydration temperature in the absence of the gas.
  • the invention contemplates alternative embodiments in which the metal hydroxide is subjected to dehydration at an elevated temperature by heating in an atmosphere comprising an acidic gas, which acts as a proton donor or induces the formation of proton donors.
  • the metal hydroxide may be heated to a temperature above that at which it normally dehydrates.
  • the acidic gas comprises a gas selected from the group consisting of: H 2 O; CO 2 ; SO 2 ; SO x ; NO 2 ; and NO x ; and mixtures of any two or more thereof.
  • the acid gas may be a mixture of an acid gas together with other, non-acid gases.
  • the present invention provides a process for separating CO 2 from a first gas stream comprising CO 2 , the process comprising the steps of:
  • step (c) calcining the metal carbonate regenerated in step (b) to regenerate the metal oxide and produce a second product gas stream comprising CO 2 ; (d) optionally repeating steps (b) and (c) using the metal oxide regenerated in step (c);
  • step (e) contacting the metal oxide regenerated in step (c) with water to form a metal hydroxide; (f) heating the metal hydroxide in a second gas stream, wherein the second gas stream comprises a gas effective to suppress the dehydration of the metal hydroxide, to a temperature that is higher than the normal decomposition temperature for the metal hydroxide; (g) dehydrating the metal hydroxide to regenerate the metal oxide;
  • step (h) optionally repeating steps (e) to (g) using the metal oxide regenerated in step (g);
  • step (i) contacting the metal oxide regenerated in step (g) with a third gas stream comprising CO 2 to carbonate the metal oxide and regenerate the metal carbonate;
  • step (J) optionally repeating steps (c) to (i) using the metal carbonate regenerated in step (i); and (Ic) repeating steps (a) to (j) using the metal carbonate regenerated in step (i).
  • the present invention provides a process for separating CO 2 from a first gas stream comprising CO 2 , the process comprising the steps of:
  • step (c) calcining the metal carbonate regenerated in step (b) to regenerate the metal oxide and produce a second product gas stream comprising CO 2 ;
  • step (d) optionally repeating steps (b) and (c) using the metal oxide regenerated in step (c); (e) contacting the metal oxide regenerated in step (c) with water to form a metal hydroxide;
  • the second gas stream comprises a gas effective to suppress the dehydration of the metal hydroxide, to a temperature that is higher than the normal decomposition temperature for the metal hydroxide, and to a temperature and for a time and at a concentration of the gas effective to suppress the dehydration of the metal hydroxide and reduce the attrition and fragmentation rates, compared to those that would otherwise occur, of the metal oxide formed upon dehydration of the metal hydroxide;
  • step (h) optionally repeating steps (e) to (g) using the metal oxide regenerated in step (g); (i) contacting the metal oxide regenerated in step (g) with a third gas stream comprising CO 2 to carbonate the metal oxide and regenerate the metal carbonate;
  • the present invention provides a process for producing a metal oxide by dehydrating a metal hydroxide, the process comprising heating the metal hydroxide in a gas stream, wherein the gas stream comprises a gas effective to suppress the dehydration of the metal hydroxide, to a temperature higher than the normal dehydration temperature for the metal hydroxide, and dehydrating the metal hydroxide to obtain the metal oxide.
  • the present invention provides a process for restoring the ability of a metal oxide to react with CO 2 , wherein the metal oxide is used in a cyclic process, wherein the metal oxide is reacted with CO 2 to form a metal carbonate and the metal carbonate is calcined to regenerate the metal oxide, the process comprising the steps of: (a) contacting the metal oxide with water to form a metal hydroxide;
  • the gas effective to suppress the dehydration of the metal hydroxide is an acidic gas.
  • the acidic gas comprises a gas selected from the group consisting of: H 2 O; CO 2 ; SO 2 ; SO x ; NO 2 ; and NO x ; and mixtures of any two or more thereof.
  • the acidic gas is CO 2 .
  • a preferred embodiment of the present invention comprises a process for producing CaO by dehydrating Ca(OH) 2 , the process comprising heating Ca(OH) 2 in a gas stream comprising CO 2 to a temperature higher than the normal dehydration temperature of Ca(OH) 2 , and dehydrating the Ca(OH) 2 to obtain CaO.
  • a further preferred embodiment of the present invention comprises a process for producing MgO by dehydrating Mg(OH) 2 , the process comprising heating Mg(OH) 2 in a gas stream comprising CO 2 to a temperature higher than the normal dehydration temperature OfMg(OH) 2 , and dehydrating the Mg(OH) 2 to obtain MgO.
  • Another preferred embodiment of the present invention comprises a process for producing a mixture of CaO and MgO by dehydrating a mixture of Ca(OH) 2 and Mg(OH) 2 , the process comprising heating a mixture Of Ca(OH) 2 and Mg(OH) 2 in a gas stream comprising CO 2 to a temperature higher than the normal dehydration temperature of the mixture of Ca(OH) 2 and Mg(OH) 2 , and dehydrating the mixture Of Ca(OH) 2 and Mg(OH) 2 to obtain a mixture of CaO and MgO.
  • Another preferred embodiment of the present invention comprises a process for producing CaO by dehydrating Ca(OH) 2 , the process comprising heating Ca(OH) 2 in a gas stream comprising 20% to 100% CO 2 to a temperature from 500°C to 620°C, and dehydrating the Ca(OH) 2 to obtain CaO.
  • Another preferred embodiment of the present invention comprises a process for producing a mixture of CaO and MgO by dehydrating a mixture of Ca(OH) 2 and Mg(OH) 2 , the process comprising heating a mixture of Ca(OH) 2 and Mg(OH) 2 in a gas stream comprising 20% to 100% CO 2 to a temperature from 500°C to 620 0 C, and dehydrating the mixture of Ca(OH) 2 and Mg(OH) 2 to obtain a mixture of CaO and MgO.
  • Another preferred embodiment of the present invention comprises a process for restoring the ability of CaO to absorb, CO 2 , wherein the CaO is used in a cyclic process, wherein the CaO is reacted with CO 2 to form CaCO 3 and CaCO 3 is calcined to regenerate CaO, the process comprising the steps of:
  • Another preferred embodiment of the present invention comprises a process for restoring the ability of MgO to absorb CO 2 , wherein the MgO is used in a cyclic process, wherein the MgO is reacted with CO 2 to form MgCO 3 and MgCO 3 is calcined to regenerate MgO, the process comprising the steps of:
  • Another preferred embodiment of the present invention comprises a process for restoring the ability of a mixture of CaO and MgO to absorb CO 2 , wherein the mixture of CaO and MgO is used in a cyclic process, wherein the mixture of CaO and MgO is reacted with CO 2 to form a mixture of CaCO 3 and MgCO 3 and the mixture of CaC ⁇ 3 and MgCO 3 is calcined to regenerate the mixture of CaO and MgO 5 the process comprising the steps of:
  • Another preferred embodiment of the present invention comprises a process for restoring the ability of a CaO to absorb CO 2 , wherein the CaO is used in a cyclic process, wherein the CaO is reacted with CO 2 to form CaCO 3 and CaCO 3 is calcined to regenerate CaO, the process comprising the steps of: (a) contacting CaO with water to form Ca(OH) 2 ;
  • Another preferred embodiment of the present invention comprises a process for restoring the ability of a mixture of CaO and MgO to absorb CO 2 , wherein the mixture of CaO and MgO is used in a cyclic process, wherein the mixture of CaO and MgO is reacted with CO 2 to form a mixture of CaCO 3 and MgCO 3 and the mixture Of CaCO 3 and MgCO 3 is calcined to regenerate the mixture of CaO and MgO, the process comprising the steps of:
  • the present invention provides apparatus adapted to perform the process of the invention.
  • apparatus adapted to perform the process of the invention.
  • Limestone was supplied by Taylors Lime, Makareao, Otago, New Zealand. The limestone was sieved, washed and then sieved between 300-600 ⁇ m.
  • a typical experiment consisted of repeated reaction cycles. Each reaction cycle started with CaO which was first hydrated, then dehydrated, then carbonated and finally calcined so that the resulting solid was also CaO.
  • the hydration of the CaO was carried out with a flowing mixture of water vapor (about 20%) and N 2 at 400 0 C. Unless otherwise specified, dehydration under fluidized bed conditions was carried out in a flow of N 2 at 450-650 0 C. Carbonation was performed in a flow OfCO 2 (20%) and N 2 at 650°C in the large reactor and, unless otherwise specified, in a flow of CO 2 (37.5%) in N 2 at 62O 0 C in the small reactor. Calcination was performed in flowing N 2 under reduced pressure at 805 0 C.
  • the initial experiment involved cycling a CaO sorbent in a fluidized bed through successive calcination-hydration-dehydration-carbonation reaction cycles and measuring the rates, the extent of the reactions, and the degree of fragmentation during the cycling. A sample was taken at the completion of every reaction cycle and examined for particle size distribution.
  • the reaction cycling regime is shown in Figure 2.
  • Table 1 illustrates the generation of fines under Cycle 4 reaction conditions expressed as cumulative percentages.
  • the rate of fragmentation based on the amount of sorbent lost to fines implies a lifetime of 40-50 cycles for the sorbent under Cycle 4 reaction conditions.
  • the data in Table 1 show that the hydration step results in substantial fragmentation of the sorbent.
  • the total amount of water captured by the sorbent was determined from the amount of water released during dehydration and captured in the water trap; however this is a fairly imprecise method.
  • the length of the run was determined by the variation of measured water vapor pressure with time.
  • the amount of CO 2 actually released was determined from the mass flow meters and calibrated by assuming that the first calcination corresponded to a 100% release of CO 2 because the initial sample was completely carbonated.
  • Table 2 shows the extent of CO 2 release for each cycle and the extent of hydration on the preceding cycle.
  • the temperature profile as a function of time is shown in Figure 5 for those carbonation/calcination cycles in which there was not a hydration step.
  • the temperature profile as a function of time was that shown in Figure 3. So the overall sequence for Cycle 5 was two carbonation-calcination reaction cycles according to the temperature profile shown in Figure 5, followed by one hydration-dehydration-carbonation-calcination reaction cycle according to the temperature profile shown in Figure 3 and so on.
  • Table 3 illustrates the generation of fines under Cycle 5 reaction conditions expressed as cumulative percentages. TABLE 3: Fines accumulation under Cycle 5 reaction conditions.
  • the Cycle 8 experiment subjected the limestone to the same periodic hydration conditions as Cycle 4, in which there was a hydration step after every calcination.
  • the final reaction cycle of this experiment included a modified dehydration step in which the Ca(OH) 2 was dehydrated in a stream of CO 2 (20%) and N 2 .
  • the same temperature profile shown in Figure 3 was used for the modified dehydration step, but the flow of CO 2 was started at minute 87 and maintained through to minute 206. This modification of the reaction conditions reduced the fragmentation levels.
  • Table 7 illustrates the generation of fines for Cycle 8 reaction conditions expressed as cumulative percentages. D/K signifies the modified dehydration step.
  • Table 9 and Figure 6 compare the fragmentation results, as shown in Tables 1 and 3, for Cycle 4 reaction conditions (periodic hydration — hydration after every calcination) and Cycle 5 reaction conditions (intermittent hydration — hydration after every three carbonation-calcination reaction cycles).
  • the sorbent materials used for the experiments under Cycle 4 and Cycle 5 reaction conditions were sourced from the same part of the quarry.
  • Tables 7 and 5 are the fragmentation results, as shown in Tables 7 and 5, for Cycle 8 reaction conditions (periodic hydration — hydration after every calcination) and Cycle 7 reaction conditions (intermittent hydration — hydration after every three carbonation-calcination reaction cycles).
  • the sorbent materials used for the experiments under Cycle 8 and Cycle 7 reaction conditions were sourced from the same part of the quarry.
  • Table 9 shows the normalized amount of fines at different points of the reaction cycles expressed as cumulative percentages.
  • the fragmentation results show that reaction conditions utilizing intermittent hydration result in reduced fragmentation levels for both limestones when compared to reaction conditions utilizing periodic hydration.
  • Table 10 shows the reaction conversions under the different reaction conditions for the different sorbents.
  • Table 11 illustrates the production of fines, in weight, and as cumulative percentages at every cycle under Cycle Pl and Cycle P2 reaction conditions.
  • the reaction conditions for Cycle P5 were identical to those for Cycle P2 but used sorbent material from a different part of the Taylors Lime quarry in a reaction sequence including intermittent hydration (every three calcinations) but in which the hydration was followed by the modified dehydration step.
  • the reaction conditions for Cycle P3 were identical to those for Cycle Pl but used a different sorbent material in a reaction sequence including intermittent hydration (hydration every three carbonations).
  • the reaction conditions for Cycle P4 were identical to those for Cycle 4 and used the same material in a reaction sequence that used periodic hydration.
  • the reaction conditions for Cycle P9 were identical to those for Cycle P2 but used a different sorbent material in a reaction sequence including intermittent hydration (every three calcinations) but in which the hydration was followed by the modified dehydration step.
  • the sorbent material for Cycle P3 was Fembrae dolomitic lime supplied by Golden Bay Cement, Portland, Northland, New Zealand.
  • the sorbent material for Cycle P9 was OmyaCal limestone supplied by Omya New Zealand Limited, Te Kuiti, Waikato, New Zealand. The sorbent material was sieved, washed and then sieved between 300-600 ⁇ m.
  • Table 12 illustrates the production of fines with a particle size of less than 150 ⁇ m as cumulative percentages and the average reaction conversions under Cycle Pl, P2, P3, P4, P5 and P9 reaction conditions. TABLE 12: Fines accumulation and average CO 2 capture under Cycle Pl, P2, P3, P4, P5 and P9 reaction conditions.
  • Cycles Pl, P2 and P4 all utilized the same sorbent material. Comparison of the data for these reaction conditions in Table 12 shows that the Cycle P2 reaction conditions, in which the reaction sequence included intermittent hydration (every three calcinations) followed by the modified dehydration step, greatly reduced the sorbent fragmentation while maintaining high CO 2 capture capacity.
  • Cycle P4 reaction conditions in which the reaction sequence includes periodic hydration, provided improved CO 2 capture activity compared to Cycle P5, in which the reaction sequence includes intermittent hydration (every three calcinations) followed by the modified dehydration step, the amount of fines produced after only 8 calcinations under Cycle P4 reaction conditions exceeded the amount produced after 76 calcinations under Cycle P5 reaction conditions.
  • the modified dehydration step follows the hydration of the CaO to Ca(OH) 2 .
  • the modified dehydration step comprised heating the Ca(OH) 2 under a flow of N 2 and CO 2 (20%) to 520°C and holding at that temperature for 22 minutes. After this step, normal cycling was resumed with a carbonation, in which the temperature was raised to 620°C under a flow of N 2 and CO 2 (20%).
  • the CaO formed from the dehydration of the Ca(OH) 2 was subsequently carbonated in a stream ofN 2 and CO 2 (20%) at 620°C.
  • the resulting material was then calcined and the CO 2 capture capacity of the CaO was measured at about 71% of the total capacity.
  • the resulting material was calcined and the CO 2 capture capacity of the CaO was measured at about 58% of the total capacity.
  • Figure 11 shows the variation with time of the temperature of the bed and the vapor pressure of water vapor leaving the bed.
  • the resulting material was then calcined. It was determined, from the amount of CO 2 released, that 15% of the material was calcium carbonate. This material must have formed in the presence of CO 2 while the material largely comprised Ca(OH) 2 . This experiment illustrates that Ca(OH) 2 does not react with CO 2 , or only reacts very slowly with CO 2 .
  • the data in Table 13 show that rate of fragmentation of CaO particles subject to successive calcination/carbonation cycles in a fluidized bed is significantly reduced by the use of the modified dehydration step, in which the Ca(OH) 2 is dehydrated in an atmosphere comprising CO 2 .
  • the data in Figure 12 and Table 13 together show that the higher the dehydration temperature of Ca(OH) 2 the lower the rate of fragmentation of CaO particles in subsequent calcination/carbonation cycles.
  • Table 14 show the effect of the modified dehydration step on the performance of the CaO sorbent.
  • “None” is a calcination/carbonation cycling process with no hydration or dehydration
  • “Normal” refers to a calcination/carbonation cycling process which includes intermittent hydration but with no CO 2 present during the dehydration step
  • “Modified” refers to a calcination/carbonation cycling process which includes intermittent hydration with 100% CO 2 present during the dehydration step.
  • TABLE 14 Effect of reactivation process on fragmentation and CO 2 capture.
  • a first cycling experiment was performed using the same reaction sequence as Cycle P2 but with a variation of the modified dehydration step.
  • a bed of freshly hydrated Ca(OH) 2 was heated at a constant rate of temperature increase of about 13°C/minute up to 620°C under a flow of N 2 and CO 2 (37.5%).
  • This modified dehydration step was followed by normal carbonation/calcination cycling as described above and the sorbent analyzed for fragmentation rate and CO 2 absorption activity.
  • the data is presented in Table 18 as Experiment P2-41.
  • a first cycling experiment was performed using the same reaction sequence as Cycle P2 but with a variation of the modified dehydration step.
  • a bed of freshly hydrated Ca(OH) 2 was heated to 52O 0 C under a flow of N 2 and CO 2 (37.5%). The temperature was held at 520°C for 23 minutes.
  • the CO 2 supply was abruptly terminated and only N 2 continued to flow.
  • the solid was held at 520 0 C under a flow of N 2 for 22 more minutes.
  • the humidity sensor recorded a significant increase in water outflow from the reactor indicating that the Ca(OH) 2 had substantially dehydrated.
  • the newly formed CaO was then subjected to normal carbonation/calcination cycling as described above and analyzed for fragmentation rate and CO 2 absoiption activity. The data are presented in Table 20 as Experiment P2-5.
  • the inhibition of the dehydration of Ca(OH) 2 is an increasing function of the concentration of CO 2 in the enveloping gas as shown in Figure 12.
  • CaO that has been formed by dehydrating Ca(OH) 2 has been shown to have restored ability of the resulting CaO to react with CO 2 gas throughout several cycles.
  • dehydration performed in the absence of CO 2 gas, or at minimal CO 2 concentration results in CaO particles that are weakened and suffer increased attrition in a fiuidized bed.
  • Dehydration of Ca(OH) 2 performed in the presence Of CO 2 and particularly when the CO 2 concentration is above 10% by mass, provides CaO particles that are more resistant to attrition in a fiuidized bed.
  • Hydrating CaO restores its capacity to capture CO 2 after several calcination/carbonation cycles, but also induces substantial fragmentation which limits the practical application of this method. Intermittent hydration reduces sorbent fragmentation compared to periodic hydration, but the fragmentation levels remain significant. Unsurprisingly, the source of the sorbent did not affect the activity levels throughout the reaction cycles. It appears that the process conditions, in particular the frequency of hydration, are the main controlling factor of the CO 2 capture activity.

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Abstract

L'invention porte sur un procédé conçu pour séparer du dioxyde de carbone de mélanges de gaz, dans lequel un sorbant d'oxyde métallique, qui est utilisé pour la capture et la libération de dioxyde de carbone, est recyclé. Le procédé incorpore la régénération de la capacité de capture du dioxyde de carbone de l'oxyde métallique pour maintenir une capacité de capture élevée sur de nombreux cycles. La régénération consiste à hydrater l'oxyde métallique puis à chauffer l'hydroxyde métallique résultant sous une atmosphère gazeuse efficace pour supprimer la déshydratation de l'hydroxyde de sorte que la déshydratation a lieu à une température élevée. La régénération peut également être utilisée indépendamment du procédé de séparation de dioxyde de carbone pour produire, à partir d'un hydroxyde métallique, un oxyde métallique ayant une résistance accrue à l'attrition et à la fragmentation.
PCT/NZ2009/000097 2008-06-05 2009-06-05 Procédé de séparation de gaz WO2009148334A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013021082A1 (fr) 2011-06-24 2013-02-14 Consejo Superior De Investigaciones Científicas (Csic) DISPOSITIF ET PROCÉDÉ PERMETTANT LA CAPTURE DE CO2 PAR CARBONATATION DE CaO
EP2722094A1 (fr) 2012-10-17 2014-04-23 Alstom Technology Ltd Système de capture de co2 à partir d'un gaz de traitement
CN106938175A (zh) * 2017-04-07 2017-07-11 青岛农业大学 一种利用镁法脱硫产物生产高浓度so2气的装置和方法
CN110305704A (zh) * 2019-05-23 2019-10-08 东南大学 一种耦合新能源低能耗实现co2捕捉与利用的系统及其方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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RU2568478C1 (ru) * 2014-09-30 2015-11-20 Федеральное государственное бюджетное учреждение "Национальный исследовательский центр "Курчатовский институт" Способ разложения карбонатов
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WO2022272186A1 (fr) * 2021-06-18 2022-12-29 Nagra Gurinder Procédé de transport de dioxyde de carbone
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1384756A (en) * 1971-08-03 1975-02-19 Harzer Dolomitwerke Gmbh Process for producing a granular filter material
US4132280A (en) * 1977-08-05 1979-01-02 Allis-Chalmers Corporation Reversibly mountable clutch control handle mounted on collapsible handle of walk-behind lawn mower
US4226839A (en) * 1978-07-21 1980-10-07 The United States Of America As Represented By The Administrator Of The U.S. Environmental Protection Agency Activation of calcium oxide as a sorbent
US5665319A (en) * 1994-07-12 1997-09-09 Director-General Of Agency Of Industrial Science And Technology Method of separating carbon dioxide from carbon dioxide containing gas and combustion apparatus having function to separate carbon dioxide from the combustion gas
US6280503B1 (en) * 1999-08-06 2001-08-28 Air Products And Chemicals, Inc. Carbon dioxide adsorbents containing magnesium oxide suitable for use at high temperatures
US6387337B1 (en) * 2000-07-14 2002-05-14 The United States Of America As Represented By The United States Department Of Energy Carbon dioxide capture process with regenerable sorbents
US20060093540A1 (en) * 2003-02-06 2006-05-04 The Ohio State University Separation of carbon dioxide (CO2) from gas mixtures by calcium based reaction separation (CaRS-CO2) process
US20070032380A1 (en) * 2003-11-14 2007-02-08 Anthony Edward J Reactivation of lime-based sorbents by co2

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1229415A (fr) * 1967-07-19 1971-04-21
DE2735436C2 (de) 1977-08-05 1984-11-29 Rohrbach, Gerhard, 7461 Dotternhausen Verfahren zur Entfernung der bei der Verbrennung fossiler Brennstoffe entstandenen Schwefeloxide aus Rauchgasen
US4312280A (en) 1980-03-13 1982-01-26 The United States Of America As Represented By The United States Department Of Energy Method of increasing the sulfation capacity of alkaline earth sorbents
US5334564A (en) 1990-07-16 1994-08-02 Board Of Trustees Operating Michigan State University Method for the preparation of highly reactive clay composites for the removal of SOx from flue gas streams
US6290921B1 (en) 1999-11-03 2001-09-18 Foster Wheeler Enegeria Oy Method and apparatus for binding pollutants in flue gas
ES2192994B1 (es) 2002-03-22 2005-02-16 Consejo Superior Investig. Cientificas Procedimiento de combustion con separacion integrada de co2 mediante carbonatacion.
JP4395570B2 (ja) 2002-07-30 2010-01-13 独立行政法人産業技術総合研究所 水の熱化学的分解による水素の製造方法
US20070092427A1 (en) 2003-11-14 2007-04-26 Anthony Edward J Pre-treatment of lime-based sorbents using hydration
US7384621B2 (en) * 2004-04-19 2008-06-10 Texaco Inc. Reforming with hydration of carbon dioxide fixing material
EP1879838A1 (fr) * 2005-04-19 2008-01-23 Inc. Carmeuse North America Services Procede de production de chaux activee a des fins d'elimination des gaz acides d'un gaz de combustion
EP1899049A4 (fr) 2005-06-28 2010-12-08 Univ Ohio State Separation de dioxyde de carbone (co2) de melange de gaz par processus de separation par reaction a base de calcium ( cars-co2)
WO2007045048A1 (fr) 2005-10-21 2007-04-26 Calix Pty Ltd Systeme et methode pour un traitement de recyclage de calcination/carbonisation
JP5293099B2 (ja) * 2007-11-14 2013-09-18 株式会社Ｉｈｉ Ｃｏ２回収ガス化方法及び装置

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1384756A (en) * 1971-08-03 1975-02-19 Harzer Dolomitwerke Gmbh Process for producing a granular filter material
US4132280A (en) * 1977-08-05 1979-01-02 Allis-Chalmers Corporation Reversibly mountable clutch control handle mounted on collapsible handle of walk-behind lawn mower
US4226839A (en) * 1978-07-21 1980-10-07 The United States Of America As Represented By The Administrator Of The U.S. Environmental Protection Agency Activation of calcium oxide as a sorbent
US5665319A (en) * 1994-07-12 1997-09-09 Director-General Of Agency Of Industrial Science And Technology Method of separating carbon dioxide from carbon dioxide containing gas and combustion apparatus having function to separate carbon dioxide from the combustion gas
US6280503B1 (en) * 1999-08-06 2001-08-28 Air Products And Chemicals, Inc. Carbon dioxide adsorbents containing magnesium oxide suitable for use at high temperatures
US6387337B1 (en) * 2000-07-14 2002-05-14 The United States Of America As Represented By The United States Department Of Energy Carbon dioxide capture process with regenerable sorbents
US20060093540A1 (en) * 2003-02-06 2006-05-04 The Ohio State University Separation of carbon dioxide (CO2) from gas mixtures by calcium based reaction separation (CaRS-CO2) process
US20070032380A1 (en) * 2003-11-14 2007-02-08 Anthony Edward J Reactivation of lime-based sorbents by co2

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2296786A4 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013021082A1 (fr) 2011-06-24 2013-02-14 Consejo Superior De Investigaciones Científicas (Csic) DISPOSITIF ET PROCÉDÉ PERMETTANT LA CAPTURE DE CO2 PAR CARBONATATION DE CaO
EP2722094A1 (fr) 2012-10-17 2014-04-23 Alstom Technology Ltd Système de capture de co2 à partir d'un gaz de traitement
CN106938175A (zh) * 2017-04-07 2017-07-11 青岛农业大学 一种利用镁法脱硫产物生产高浓度so2气的装置和方法
CN110305704A (zh) * 2019-05-23 2019-10-08 东南大学 一种耦合新能源低能耗实现co2捕捉与利用的系统及其方法

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US20110158874A1 (en) 2011-06-30
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